WO2021020243A1 - Pigment composite, support d'identification, et procédé de jugement d'authentification - Google Patents

Pigment composite, support d'identification, et procédé de jugement d'authentification Download PDF

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Publication number
WO2021020243A1
WO2021020243A1 PCT/JP2020/028316 JP2020028316W WO2021020243A1 WO 2021020243 A1 WO2021020243 A1 WO 2021020243A1 JP 2020028316 W JP2020028316 W JP 2020028316W WO 2021020243 A1 WO2021020243 A1 WO 2021020243A1
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liquid crystal
cholesteric liquid
pigment
crystal pigment
selective reflection
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PCT/JP2020/028316
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English (en)
Japanese (ja)
Inventor
将 相松
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日本ゼオン株式会社
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Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to CN202080053840.8A priority Critical patent/CN114207084A/zh
Priority to JP2021536979A priority patent/JPWO2021020243A1/ja
Priority to EP20846442.0A priority patent/EP4006107A4/fr
Priority to US17/629,861 priority patent/US20220275213A1/en
Publication of WO2021020243A1 publication Critical patent/WO2021020243A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/50—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing steroidal liquid crystal compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0034—Mixtures of two or more pigments or dyes of the same type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/364—Liquid crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/107—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azomethine dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • G07D7/12—Visible light, infrared or ultraviolet radiation
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • G07D7/12—Visible light, infrared or ultraviolet radiation
    • G07D7/1205—Testing spectral properties

Definitions

  • the present invention relates to a composite pigment, an identification medium, and an authenticity determination method.
  • the cholesteric liquid crystal resin is obtained by cholesteric orientation of a liquid crystal compound and curing while maintaining the orientation.
  • a cholesteric liquid crystal resin has a circular polarization separation function that reflects one of the left and right circularly polarized light and transmits the other circularly polarized light. It is known that in the cholesteric liquid crystal resin material, the wavelength of the reflected circular polarization shifts to the short wavelength side as the viewing angle ⁇ from the front direction increases. Using this property, the authenticity of the identification medium using the cholesteric liquid crystal resin can be identified.
  • the present inventor uses a composite pigment containing a specific first cholesteric liquid crystal pigment and a specific second cholesteric liquid crystal pigment in a predetermined ratio, and is derived from the first cholesteric liquid crystal pigment. It was found that the color of the above color is not visible or difficult to see by visual observation, but it can be made visible by microscopic observation, and thus the anti-counterfeiting effect can be improved.
  • the first cholesteric liquid crystal pigment a pigment having a central wavelength of the selective reflection band within a wavelength range of 400 nm or more and 800 nm or less and having a selective reflection bandwidth of 150 nm or less is used, and the second cholesteric liquid crystal pigment is used.
  • the present invention provides the following.
  • a first cholesteric liquid crystal pigment and a second cholesteric liquid crystal pigment are included.
  • the first cholesteric liquid crystal pigment is a pigment having a central wavelength of the selective reflection band within a wavelength range of 400 nm or more and 800 nm or less and having a selective reflection bandwidth of 150 nm or less.
  • the second cholesteric liquid crystal pigment is a pigment having a selective reflection bandwidth of 200 nm or more within a wavelength range of 400 nm or more and 800 nm or less. At least a part of the selective reflection band of the first cholesteric liquid crystal pigment and the selective reflection band of the second cholesteric liquid crystal pigment overlap.
  • Authenticity determination including step 3 of observing the identification medium with a microscope and determining whether or not both the color derived from the first cholesteric liquid crystal pigment and the color derived from the second cholesteric liquid crystal pigment are visible.
  • the present invention it is possible to provide a composite pigment having an improved anti-counterfeiting effect, an ink composition and an identification medium using the composite pigment, and a method for identifying the authenticity of the identification medium.
  • FIG. 1 is a front view schematically showing an apparatus for producing a stripped piece of a resin thin film used in the production of the composite pigment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing a cross section when a corner portion of a bar of the manufacturing apparatus of FIG. 1 is cut by a plane perpendicular to the width direction of the support.
  • composition includes not only a mixture of two or more substances, but also a material consisting of a single substance, and an “agent” is a material consisting of a single substance. Others include mixtures of two or more substances.
  • (meth) acrylate means “acrylate”, “methacrylate”, or both.
  • (meth) acrylic means “acrylic", “methacrylic”, or both.
  • (Thio) Epoxy means “epoxy”, “thioepoxy”, or both.
  • iso (thio) cyanate means “isocyanate”, “isothiocyanate”, or both.
  • the composite pigment of the present invention includes a first cholesteric liquid crystal pigment and a second cholesteric liquid crystal pigment.
  • the first cholesteric liquid crystal pigment is a pigment having a central wavelength of the selective reflection band within a wavelength range of 400 nm or more and 800 nm or less, and having a selective reflection bandwidth of 150 nm or less.
  • the second cholesteric liquid crystal pigment is a pigment having a selective reflection bandwidth of 200 nm or more within a wavelength range of 400 nm or more and 800 nm or less. At least a part of the selective reflection band of the first cholesteric liquid crystal pigment and the selective reflection band of the second cholesteric liquid crystal pigment overlap.
  • the content of the first cholesteric liquid crystal pigment is more than 0% by weight and 30% by weight or less with respect to the total amount of the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment.
  • the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment are each composed of a cholesteric liquid crystal resin.
  • the "cholesteric liquid crystal resin” means a resin material having cholesteric regularity, and means that the molecules or molecular portions constituting the resin are aligned in a state having cholesteric regularity in the resin.
  • the term "molecules in the resin have cholesteric regularity” means that the molecules in the resin have the specific regularity described below.
  • the orientation direction in the next third plane that further overlaps the second plane deviates from the orientation direction in the second plane at a slight angle.
  • the angles of the molecular axes in the planes are sequentially shifted (twisted).
  • the structure in which the direction of the molecular axis is twisted in this way becomes an optically chiral structure.
  • the cholesteric liquid crystal resin having an optically chiral structure usually has a circular polarization selective reflection function that selectively reflects circular polarization.
  • Cholesteric liquid crystal resin "selectively reflects" light in a predetermined wavelength range means that one of the unpolarized light (that is, natural light) in a predetermined wavelength range is reflected and the other circularly polarized component is reflected. It means to be transparent.
  • the "selective reflection band” refers to the range of wavelengths of circularly polarized light that is selectively reflected.
  • the “selective reflection bandwidth” is the width of the selective reflection band, and specifically, it can be a half width of the selective reflection band.
  • the selective reflection band of the first cholesteric liquid crystal pigment and the selective reflection band of the second cholesteric liquid crystal pigment overlap.
  • the range in which the selective reflection band of the first cholesteric liquid crystal pigment and the selective reflection band of the second cholesteric liquid crystal pigment overlap is preferably 80% or more, more preferably 80% or more of the entire selective reflection band of the first cholesteric liquid crystal pigment. It is 90% or more, more preferably 100%.
  • the range in which the selective reflection band of the first cholesteric liquid crystal pigment and the selective reflection band of the second cholesteric liquid crystal pigment overlap is preferably 10% or more, more preferably 10% or more, based on the entire selective reflection band of the second cholesteric liquid crystal pigment. It is 20% or more, preferably 50% or less, and more preferably 40% or less.
  • the overlapping range of the selective reflection band of the first cholesteric liquid crystal pigment and the selective reflection band of the second cholesteric liquid crystal pigment is equal to or more than the above lower limit value with respect to the entire selective reflection band of the first cholesteric liquid crystal pigment, it is visually observed.
  • the anti-counterfeiting effect is enhanced.
  • the overlapping range of the selective reflection band of the first cholesteric liquid crystal pigment and the selective reflection band of the second cholesteric liquid crystal pigment is equal to or more than the above lower limit value with respect to the entire selective reflection band of the second cholesteric liquid crystal pigment, in visual observation, Since it becomes difficult to recognize the difference between the color derived from the first cholesteric liquid crystal pigment and the color derived from the second cholesteric liquid crystal pigment, the anti-counterfeiting effect is enhanced. Further, when it is not more than the above upper limit value, the difference in color between the first cholesteric pigment and the second cholesteric liquid crystal pigment can be easily recognized by microscopic observation.
  • the selective reflection bandwidth of the first cholesteric liquid crystal pigment is 150 nm or less, and the selective reflection bandwidth of the second cholesteric liquid crystal pigment is 200 nm or more. That is, the first cholesteric liquid crystal pigment is a cholesteric liquid crystal pigment having a narrower (narrower band) selective reflection bandwidth than the second cholesteric liquid crystal pigment, and the second cholesteric liquid crystal pigment has a selective reflection band than that of the first cholesteric liquid crystal pigment.
  • a wide (broadband) cholesteric liquid crystal pigment When the identification medium using the cholesteric liquid crystal pigment having a narrow selective reflection band width is observed with natural light, the appearance having colors corresponding to the reflection band can be visually recognized.
  • the composite pigment includes a first cholesteric liquid crystal pigment having a selective reflection bandwidth of 150 nm or less and a second cholesteric liquid crystal pigment having a selective reflection bandwidth of 200 nm or more, such a composite pigment is used.
  • the visually recognizable color is the color derived from the first cholesteric liquid crystal pigment or the second cholesteric liquid crystal pigment.
  • the selective reflection bandwidth of the first cholesteric liquid crystal pigment is preferably 120 nm or less, more preferably 110 nm or less, preferably 30 nm or more, and more preferably 50 nm or more.
  • the selective reflection bandwidth of the second cholesteric liquid crystal pigment is preferably 200 nm or more, more preferably 300 nm or more.
  • the upper limit of the selective reflection bandwidth of the second cholesteric liquid crystal pigment is not particularly limited, but is preferably 2000 nm or less and 1000 nm or less.
  • the first cholesteric liquid crystal pigment has a central wavelength of the selective reflection band within a wavelength range of 400 nm or more and 800 nm or less.
  • the central wavelength of the selective reflection band of each cholesteric liquid crystal pigment can be the central wavelength of the region related to the half width of the selective reflection band. That is, the reflection spectrum of the cholesteric liquid crystal pigment at an incident angle of 5 ° is measured, and in the obtained reflection spectrum, the peak having the maximum intensity and the base having the minimum intensity are determined, and the minimum intensity + (maximum intensity-minimum intensity) /.
  • the wavelength ⁇ 1 on the short wavelength side and the wavelength ⁇ 2 on the long wavelength side of the peak, which show the intensity of 2 are obtained.
  • the average value (( ⁇ 1 + ⁇ 2) / 2) of these can be obtained, and the average value can be used as the center wavelength.
  • the selective reflection band of each cholesteric liquid crystal pigment ranges from the wavelength ⁇ 1 on the short wavelength side of the peak showing the intensity of minimum intensity + (maximum intensity-minimum intensity) / 2 in the reflection spectrum to the wavelength ⁇ 2 on the long wavelength side. It is in the range ( ⁇ 1 to ⁇ 2), and the selective reflection bandwidth of each cholesteric liquid crystal pigment is the difference ( ⁇ 2- ⁇ 1) between the wavelength ⁇ 2 on the long wavelength side and the wavelength ⁇ 1 on the short wavelength side.
  • the central wavelength of the selective reflection band of each cholesteric liquid crystal pigment is a thin film containing the pigment. Is the central wavelength of the selective reflection band observed when the is formed.
  • the central wavelength ⁇ (nm) of the selective reflection band has an average refractive index of n for the cholesteric liquid crystal resin and a chiral structure possessed by the cholesteric liquid crystal resin.
  • the pitch length of the (spiral structure) is P (nm)
  • ⁇ n ⁇ P ⁇ cos ⁇
  • the wavelength is shorter than the central wavelength ⁇ of the band.
  • the front direction of the thin film containing the cholesteric liquid crystal pigment means the normal direction of the thin film when the thin film containing the cholesteric liquid crystal pigment is formed.
  • the central wavelength ⁇ of the selective reflection band when the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment are observed from the front with a viewing angle ⁇ can be increased by increasing the pitch length P of the chiral structure (spiral structure), for example. It can be made smaller by reducing the pitch length P.
  • Examples of the method of adjusting the pitch length of each cholesteric liquid crystal resin include a method of adjusting the type of chiral agent and a method of adjusting the amount of the chiral agent.
  • the content of the first cholesteric liquid crystal pigment is more than 0% by weight and 30% by weight or less with respect to the total amount of the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment.
  • the content of the first cholesteric liquid crystal pigment is preferably 10% by weight or more, more preferably 15% by weight or more, preferably 25% by weight or less, based on the total amount of the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment. It is preferably 20% by weight or less.
  • the content of the first cholesteric liquid crystal pigment with respect to the total amount of the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment is not more than the above upper limit value, is the color derived from the first cholesteric liquid crystal pigment not visually recognized by visual observation? Although it is difficult to see, the color derived from the second cholesteric liquid crystal pigment can be visually recognized, and both the color derived from the first cholesteric liquid crystal pigment and the color derived from the second cholesteric liquid crystal pigment can be visually recognized by microscopic observation. Thereby, the anti-counterfeiting effect can be improved.
  • the color derived from the second cholesteric liquid crystal pigment and the first cholesteric are observed under a microscope.
  • the color derived from the liquid crystal pigment can be visually recognized.
  • the average particle size of the flakes is preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, preferably 120 ⁇ m or less, more preferably. Is 100 ⁇ m or less, particularly preferably 80 ⁇ m or less.
  • the particle size distribution can be measured by a laser / scattering method, and the average particle size can be measured from the particle size distribution.
  • the particle size at which the integrated value of the volume is 50% can be used as the average particle size.
  • the average particle size of flakes is a volume average unless otherwise specified.
  • the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment may have the same twisting direction as each other, or may have different twisting directions from each other.
  • the twisting direction can be determined by observing the reflected light when unpolarized light is incident on the sample containing each cholesteric liquid crystal pigment through the left and right circularly polarizing plates. That is, the twisting direction can be determined by irradiating the sample with non-polarized light from the observer side and observing the reflected light reflected by the sample and reaching the observer side.
  • the reflected light is right-handed circularly polarized light, it can be judged as a right-handed twist, and when it is left-handed circularly polarized light, it can be judged as a left-handed twist.
  • the cholesteric liquid crystal resin used as a material for the first cholesteric liquid crystal pigment is a cured product of the first liquid crystal composition containing a liquid crystal compound.
  • the cholesteric liquid crystal resin used as a material for the second cholesteric liquid crystal pigment is a cured product of the second liquid crystal composition containing a liquid crystal compound.
  • a polymerizable liquid crystal compound is preferable.
  • a liquid crystal composition containing a liquid crystal compound having polymerizability can be easily cured while maintaining an oriented state by polymerizing the liquid crystal compound.
  • a cholesteric liquid crystal compound As the liquid crystal compound, a cholesteric liquid crystal compound can be used.
  • the cholesteric liquid crystal compound is a compound capable of exhibiting cholesteric liquid crystal property.
  • a liquid crystal composition containing such a cholesteric liquid crystal compound and curing the liquid crystal composition in a state of exhibiting the cholesteric liquid crystal phase a cholesteric liquid crystal resin which is a resin material having cholesteric regularity can be obtained.
  • liquid crystal compound contained in the first liquid crystal composition and the second liquid crystal composition for example, a rod-shaped liquid crystal compound having two or more reactive groups in one molecule can be used.
  • the rod-shaped liquid crystal compound include a compound represented by the formula (1). R 3- C 3- D 3- C 5- MC 6- D 4- C 4- R 4 Equation (1)
  • R 3 and R 4 are reactive groups, which are independently a (meth) acrylic group, a (thio) epoxy group, an oxetane group, a thietanyl group, an aziridinyl group, a pyrrol group, and a vinyl group. , Allyl group, fumarate group, cinnamoyl group, oxazoline group, mercapto group, iso (thio) cyanate group, amino group, hydroxyl group, carboxyl group, and alkoxysilyl group. By having these reactive groups, it is possible to obtain a cholesteric liquid crystal resin having high strength when the liquid crystal composition is cured.
  • D 3 and D 4 are independently single-bonded, linear or branched-chain alkyl groups having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Represents a group selected from the group consisting of linear or branched alkylene oxide groups.
  • C 3 to C 6 are independently single-bonded, -O-, -S-, -SS-, -CO-, -CS-, -OCO-, and -CH 2.
  • M represents a mesogen group. Specifically, M may have an unsubstituted or substituent, azomethines, azoxys, phenyls, biphenyls, terphenyls, naphthalenes, anthracenes, benzoic acid esters, cyclohexanecarboxylics.
  • R 5 and R 7 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms which may have a substituent examples include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an amino group, and 1 to 10 carbon atoms.
  • Examples thereof include an alkylcarbonyloxy group having 7 to 7 groups and an alkoxycarbonyloxy group having 2 to 7 carbon atoms.
  • the rod-shaped liquid crystal compound preferably has an asymmetric structure.
  • the asymmetric structure is a structure in which R 3- C 3- D 3- C 5- and -C 6- D 4- C 4- R 4 are different from each other with the mesogen group M as the center in the formula (1).
  • the orientation uniformity can be further enhanced.
  • rod-shaped liquid crystal compound examples include the following compounds (B1) to (B9).
  • one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.
  • the first liquid crystal composition and / or the second liquid crystal composition preferably contains a compound represented by the above formula (1) as a liquid crystal compound, and one or more selected from the above compounds (B1) to (B9). It is more preferable to include.
  • the first liquid crystal composition and / or the second liquid crystal composition may contain a compound represented by the following formula (2) in addition to the liquid crystal compound.
  • the compound of formula (2) can function as an orientation aid.
  • R 1 and R 2 are independently linear or branched alkyl groups having 1 to 20 carbon atoms and linear having 1 to 20 carbon atoms, respectively.
  • a branched alkylene oxide group, a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, or a (meth) acrylic group, an epoxy group, a mercapto group, an isocyanate group, an amino group, which may be mediated by any bonding group may be present.
  • a group selected from the group consisting of cyano groups may be present.
  • the alkyl group and the alkylene oxide group may not be substituted or may be substituted with one or more halogen atoms.
  • the halogen atom, hydroxyl group, carboxyl group, (meth) acrylic group, epoxy group, mercapto group, isocyanate group, amino group and cyano group are alkyl groups having 1 to 2 carbon atoms and alkylene oxides. It may be bonded to a group.
  • R 1 and R 2 include halogen atoms, hydroxyl groups, carboxyl groups, (meth) acrylic groups, epoxy groups, mercapto groups, isocyanate groups, amino groups, and cyano groups.
  • At least one of R 1 and R 2 is preferably a reactive group.
  • the compound represented by the formula (2) can be fixed in the cholesteric liquid crystal resin at the time of curing to form a stronger resin.
  • the reactive group include a carboxyl group, a (meth) acrylic group, an epoxy group, a mercapto group, an isocyanate group, and an amino group.
  • a 1 and A 2 are independently 1,4-phenylene group, 1,4-cyclohexylene group, cyclohexene-1,4-ylene group, 4,4'-biphenylene group, 4 , 4'-bicyclohexene group, and 2,6-naphthylene group represents a group selected from the group.
  • substituents such as a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, and an alkyl halide group. You may be. If two or more substituents are present in each of A 1 and A 2 , they may be the same or different.
  • a 1 and A 2 are groups selected from the group consisting of 1,4-phenylene groups, 4,4'-biphenylene groups, and 2,6-naphthylene groups. These aromatic ring skeletons are relatively rigid as compared with the alicyclic skeleton, have a high affinity for the rod-shaped liquid crystal compound mesogen, and have higher orientation uniformity.
  • particularly preferable compounds represented by the formula (2) include the following compounds (A1) to (A10). One of these may be used alone, or two or more of them may be used in combination at any ratio. Among the following compounds (A1) to (A10), one or more selected from the compounds (A2) and (A10) is particularly preferable.
  • the compounds (A2) and (A10) can lower the development temperature of the liquid crystal phase in the liquid crystal composition, and can maintain a wide temperature range in which the liquid crystal phase of the liquid crystal compound is exhibited.
  • the weight ratio represented by (total weight of the compound represented by the formula (2)) / (total weight of the rod-shaped liquid crystal compound) in the first liquid crystal composition or the second liquid crystal composition is preferably 0.05 or more. It is more preferably 0.1 or more, particularly preferably 0.15 or more, preferably 1 or less, more preferably 0.65 or less, and particularly preferably 0.55 or less.
  • the weight ratio is preferably 0.05 or more. It is more preferably 0.1 or more, particularly preferably 0.15 or more, preferably 1 or less, more preferably 0.65 or less, and particularly preferably 0.55 or less.
  • the total weight of the compounds represented by the formula (2) indicates the weight when only one kind of the compound represented by the formula (2) is used, and when two or more kinds are used, the total weight is shown. Shows the total weight.
  • the total weight of the rod-shaped liquid crystal compounds indicates the weight when only one type of rod-shaped liquid crystal compound is used, and indicates the total weight when two or more types are used.
  • the molecular weight of the compound represented by the formula (2) is preferably less than 600, and the molecular weight of the rod-shaped liquid crystal compound is preferably less than 600. It is preferably 600 or more.
  • the compound represented by the formula (2) can enter the gaps of the rod-shaped liquid crystal compound having a larger molecular weight than that, so that the orientation uniformity can be improved.
  • the first liquid crystal composition and the second liquid crystal composition may each contain a chiral agent.
  • the twisting direction of the cholesteric liquid crystal resin can be appropriately selected depending on the type and structure of the chiral agent used.
  • Specific examples of the chiral agent include JP-A-2005-289881, JP-A-2004-115414, JP-A-2003-66214, JP-A-2003-313187, JP-A-2003-342219, and JP-A-2003-342219. It is possible to appropriately use those published in JP-A-2000-290315, JP-A-6-072962, US Pat. No. 6,468,444, International Publication No. 98/00428, JP-A-2007-176870, and the like.
  • LC756 of BASF Palio Color
  • chiral agent a compound represented by the following formula (3) can also be used.
  • One type of chiral agent may be used alone, or two or more types may be used in combination at any ratio.
  • the amount of chiral agent can be arbitrarily set within a range that does not deteriorate the desired optical performance.
  • the specific amount of the chiral agent is usually 1% by weight to 60% by weight in the liquid crystal composition.
  • the first liquid crystal composition and the second liquid crystal composition may each contain a polymerization initiator.
  • the polymerization initiator include photopolymerization initiators, and compounds capable of generating radicals or acids by ultraviolet rays or visible light can be used.
  • Specific examples of the photopolymerization initiator include benzoin, benzyl dimethyl ketal, benzophenone, biacetyl, acetophenone, Michler ketone, benzyl, benzyl isobutyl ether, tetramethylthium mono (di) sulfide, 2,2-azobisisobutyronitrile, and the like.
  • 2,2-azobis-2,4-dimethylvaleronitrile benzoyl peroxide, di-tert-butyl peroxide, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one , 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, methylbenzoylformate, 2,2 -Diethoxyacetophenone, ⁇ -ionone, ⁇ -bromostyrene, diazoaminobenzene, ⁇ -amylcinnamic aldehyde, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, pp'-dichlorobenzophenone, pp'-
  • IRGACURE 184 or IRGACURE OXE02 manufactured by BASF can also be used. One of these may be used alone, or two or more of them may be used in combination at any ratio. Further, if necessary, a known photosensitizer or a tertiary amine compound as a polymerization accelerator may be used to control the curability.
  • the amount of the polymerization initiator is preferably 0.03% by weight to 7% by weight in the liquid crystal composition.
  • the first liquid crystal composition and the second liquid crystal composition may each contain a surfactant as a leveling agent.
  • a surfactant for example, one that does not inhibit the orientation can be appropriately selected and used.
  • a surfactant for example, a nonionic surfactant containing a siloxane or an alkyl fluoride group in the hydrophobic group portion is preferably mentioned.
  • oligomers having two or more hydrophobic group portions in one molecule are particularly preferable.
  • surfactants include PF-151N, PF-636, PF-6320, PF-656, PF-6520, PF-3320, PF-651, PF-652 of PolyFox of OMNOVA; FTX-209F, FTX-208G, FTX-204D; Surfron KH-40, S420; etc. of Seimi Chemical Co., Ltd. can be used.
  • one type of surfactant may be used alone, or two or more types may be used in combination at an arbitrary ratio.
  • the amount of the surfactant is preferably such that the amount of the surfactant in the cholesteric liquid crystal resin is 0.05% by weight to 3% by weight.
  • Each of the first liquid crystal composition and the second liquid crystal composition may further contain an arbitrary component, if necessary.
  • the optional component include; a polymerization inhibitor for improving pot life; an antioxidant for improving durability, an ultraviolet absorber and a light stabilizer; and the like.
  • one of these optional components may be used alone, or two or more of them may be used in combination at an arbitrary ratio. The amount of these arbitrary components can be arbitrarily set as long as the desired optical performance is not deteriorated.
  • the method for producing the first liquid crystal composition and the second liquid crystal composition is not particularly limited, and the first liquid crystal composition and the second liquid crystal composition can be produced by mixing the above components, respectively.
  • the first cholesteric liquid crystal pigment is prepared by applying a coating liquid containing the first liquid crystal composition and a solvent on an appropriate support and drying as necessary to form a layer of the first liquid crystal composition, and this layer is cured. This can be produced by forming a thin film of the first cholesteric liquid crystal resin, then peeling the thin film of the first cholesteric liquid crystal resin from the support, and crushing the thin film.
  • the surface of the support Prior to the application of the coating liquid containing the first liquid crystal composition, the surface of the support may be subjected to a treatment for imparting an orientation regulating force.
  • a treatment for imparting an orientation regulating force include rubbing treatment on the surface of the support, stretching treatment of the film of the support, and the like.
  • a surface treatment such as a corona treatment may be performed in order to enhance the affinity between the surface of the support and the first liquid crystal composition.
  • a film having a resin layer made of resin can be used as the support.
  • polymers contained in the resin constituting the resin layer include chain olefin polymers, cycloolefin polymers, polycarbonates, polyesters, polysulfones, polyethersulfones, polystyrenes, polyvinyl alcohols, cellulose acetate-based polymers, and polychlorides. Examples include vinyl and polymethacrylate.
  • the resin one containing one kind of polymer alone may be used, or one containing two or more kinds of polymers in combination at an arbitrary ratio may be used.
  • the resin may contain any compounding agent as long as the effects of the present invention are not significantly impaired.
  • the support may be a single-layer structure film having only one layer, or a multi-layer structure film having two or more layers. Therefore, the support may be a film having only the above-mentioned resin layer, or may be a film having an arbitrary layer in addition to the above-mentioned resin layer.
  • the support may have an alignment film on its surface.
  • the alignment film can be formed of, for example, a resin containing a polymer such as polyimide, polyvinyl alcohol, polyester, polyarylate, polyamideimide, polyetherimide, or polyamide. In addition, one of these polymers may be used alone, or two or more of these polymers may be used in combination at any ratio.
  • the alignment film can be produced by applying a solution containing the above-mentioned polymer, drying, and applying a rubbing treatment.
  • the thickness of the alignment film is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 5 ⁇ m or less, and more preferably 1 ⁇ m or less.
  • the support may be an unstretched unstretched film or a stretched stretched film. Further, the support may be an isotropic film or an anisotropic film. Further, the support may be surface-treated on one side or both sides thereof. By applying the surface treatment, it is possible to improve the adhesion with other layers directly formed on the surface of the support. Examples of the surface treatment include energy ray irradiation treatment and chemical treatment.
  • the thickness of the support is preferably 30 ⁇ m or more, more preferably 60 ⁇ m or more, preferably 300 ⁇ m or less, and more preferably 200 ⁇ m or less from the viewpoints of handleability during manufacturing, material cost, thinning and weight reduction. ..
  • the coating liquid containing the first liquid crystal composition can be applied by a known coating method.
  • the coating method include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method, a spin coating method, and a bar coating method.
  • orientation treatment can be performed if necessary before performing the curing step.
  • the orientation treatment can be performed, for example, by heating the layer of the first liquid crystal composition at 50 to 150 ° C. for 0.5 to 10 minutes. By performing the orientation treatment, the liquid crystal compound in the first liquid crystal composition can be well oriented.
  • the treatment of curing the layer of the first liquid crystal composition can be performed by irradiating with energy rays one or more times.
  • energy rays include ultraviolet light, visible light and other electromagnetic waves.
  • the energy ray irradiation can be performed by irradiating light having a wavelength of 200 to 500 nm for 0.01 seconds to 3 minutes.
  • the method of peeling and crushing the thin film of the first cholesteric liquid crystal resin from the support is not particularly limited, and examples thereof include the method described in JP-A-2015-27743.
  • the thin film of the first cholesteric liquid crystal resin can be peeled from the support by using the peeling piece manufacturing apparatus shown in FIG.
  • a method for peeling the thin film of the first cholesteric liquid crystal resin using the apparatus shown in FIG. 1 will be described.
  • the "thin film of the first cholesteric liquid crystal resin” is also simply referred to as the "first resin thin film”.
  • FIG. 1 is a front view schematically showing an apparatus for producing a stripped piece of a resin thin film used in the production of the composite pigment of the present invention.
  • the peeling piece manufacturing apparatus 100 shown in FIG. 1 includes a film delivery unit 120 capable of delivering a multilayer film 110 including a support 111 and a first resin thin film (see 112 in FIG. 2), and the fed multilayer.
  • a peeling unit 130 capable of peeling the first resin thin film 112 from the film 110 and a collecting unit 140 capable of recovering the support 111 from which the first resin thin film 112 has been peeled are provided.
  • the peeling portion 130 includes a bar 134 having a corner portion 135 provided at an acute angle, and a nozzle 136 provided immediately downstream of the corner portion 135 that can inject air.
  • the angle of the corner portion 135 of the bar 134 is set so that the multilayer film 110 can be folded back at an angle ⁇ , and the corner portion has a chamfered structure.
  • the peeling of the first resin thin film using the apparatus 100 can be performed as follows.
  • the multilayer film 110 is attached to the film delivery portion 120 so that the first resin thin film 112 can be removed from the support 111 at the corner portion 135 of the bar 134 and the multilayer film 110 can be folded back.
  • the multilayer film 110 is sent out from the film feeding unit 120 in a state where the film collecting unit 140 applies tension to the multilayer film 10 in the transport direction.
  • the multilayer film 110 sent out from the film delivery unit 120 enters the peeling chamber 131 through the slit 132 and is folded back at the corner portion 135 of the bar 134.
  • the support 111 bent at the corner portion 135 usually does not break.
  • the first resin thin film 112 bent at the corner portion 135 is stressed by the bending deformation, and the first resin thin film 112 is destroyed by this stress to form a crack 113.
  • the first resin thin film 112 having cracks formed by the air ejected from the nozzle 136 is peeled off and blown off to become a peeled piece 114.
  • a part of the peeling piece 114 separates from the support 111 and is sent to the recovery path according to the flow of air injected by the nozzle 136. Further, another part of the peeling piece 114 is carried together with the support 111 in a state of being placed on the support 111 or attached to the support 111 by a force such as electrostatic attraction.
  • the support 111 from which the first resin thin film 112 has been peeled off at the corner portion 135 of the bar 134 is transported downstream. As shown in FIG. 1, when the support 111 comes to the nozzle 136 installation position, the air ejected from the nozzle 136 is blown to the cracked portion of the first resin thin film 112. By this air, the peeling piece 114 contained in the cracked portion of the first resin thin film 112 is blown off and sent to the recovery path 137. Further, the first resin thin film (not shown) that remained on the support 111 without being separated from the support 111 only by forming the crack 113 is also supported by the pressure of the air jetted from the nozzle 136. It is peeled from 111, becomes a peeled piece 114, and is sent to the collection path 137.
  • the peeled piece 114 sent to the collection path 137 is sent to a collector (not shown) on the air stream and collected.
  • the support 111 from which the first resin thin film 112 has been peeled off is conveyed to the film recovery unit 140 through the slit 133, wound around the winding core 141, and recovered.
  • the first cholesteric liquid crystal pigment having a desired particle size is obtained by pulverizing the peeled pieces of the first cholesteric liquid crystal resin peeled from the support.
  • the crushing process is usually carried out using a crusher.
  • the crusher include a ball mill, a bead mill, a roll mill, a rod mill, a jet mill, a stone mill type crusher and the like.
  • the second cholesteric liquid crystal pigment can be produced by forming a thin film of the second cholesteric liquid crystal resin on the support, peeling the thin film of the second cholesteric liquid crystal resin from the support, and crushing the thin film.
  • the operation of curing the layer of the second liquid crystal composition in a state where the pitch of the spiral structure is continuously changed by light irradiation and / or heating treatment at least once is performed on the thin film of the cholesteric liquid crystal resin. Since it is an operation to expand the reflection band, it is called a wide band processing. By performing the wide band processing, a wide reflection band can be realized even with a thin film of cholesteric liquid crystal resin having a thin thickness of, for example, 5 ⁇ m or less.
  • the peeling and crushing of the thin film of the second cholesteric liquid crystal resin is carried out in place of the thin film of the first cholesteric liquid crystal resin (first resin thin film) in the above-mentioned "peeling and crushing of the thin film of the first cholesteric liquid crystal resin". This can be done by using a thin film of resin.
  • the ink composition contains the composite pigment of the present invention and a binder resin.
  • the binder resin contains a polymer. Examples of such a polymer include a polyester polymer, an acrylic polymer, a polystyrene polymer, a polyamide polymer, a polyurethane polymer, a polyolefin polymer, and a polycarbonate polymer. Examples include coalescence and polyvinyl-based polymers.
  • One type of binder resin may be used alone, or two or more types may be used in combination at any ratio.
  • the method for producing the ink composition of the present invention is not particularly limited, and the ink composition can be produced by mixing the above components.
  • the ink composition of the present invention can form an identification medium by forming an ink layer by printing on a substrate and then curing the ink layer.
  • the material of the base material forming the ink layer is not particularly limited, and examples thereof include resin, metal, glass, and paper.
  • the printing method of the ink composition is not particularly limited, and examples thereof include screen printing, gravure printing, flexographic printing, letterpress printing, and offset printing.
  • the treatment of curing the ink layer can be performed by heating or irradiating with energy rays one or more times.
  • An example of heating is heat treatment at 150 ° C. or higher.
  • thermosetting the ink layer by heat treatment it is possible to obtain an identification medium in which a printing layer containing the composite pigment of the present invention is formed on a base material.
  • energy rays include ultraviolet light, visible light and other electromagnetic waves.
  • the energy ray irradiation can be performed by irradiating light having a wavelength of 200 to 500 nm for 0.01 seconds to 3 minutes.
  • the curing treatment of the ink layer it is possible to obtain an identification medium in which a printing layer containing the composite pigment of the present invention is formed on a base material.
  • the identification medium of the present invention contains a binder resin and a pigment dispersed in the binder resin.
  • the pigment contained in the identification medium is the composite pigment of the present invention.
  • the identification medium may be in an embodiment including a binder resin and a layer containing the composite pigment of the present invention dispersed in the binder resin, and an arbitrary layer.
  • the arbitrary layer include a base material and an adhesive layer.
  • As the material of the base material 2. Examples include the materials described in.
  • the arbitrary layer is preferably a layer having high light transmittance, more preferably a layer having a total light transmittance of 70% or more, and also.
  • a layer having a small in-plane retardation Re (for example, 5 nm or less) is preferable.
  • the identification medium is suitably used for identifying the authenticity of an article by attaching it to an article, transferring it, or the like.
  • articles whose authenticity should be identified include articles such as cash vouchers, gift certificates, tickets, certificates, and security cards.
  • the identification medium can also be used in the form of a label, a sticker, or the like for authenticity identification.
  • the method for determining the authenticity of the identification medium of the present invention is one type selected from the hue, lightness, and saturation of the reflected light by observing the reflected light from the identification medium through the left circular polarizing plate and the right circular polarizing plate.
  • the step 1 of determining whether or not there is a difference, the step 2 of visually observing the identification medium and determining whether or not the color derived from the second cholesteric liquid crystal pigment is visible, and the identification medium are microscopically arranged.
  • step 1 the reflected light from the identification medium is observed through the left circular polarizing plate and the right circular polarizing plate, and whether or not there is a difference in one or more types selected from the hue, lightness, and saturation of the reflected light. Is a step of determining.
  • the identification medium contains a binder resin and a pigment dispersed in the binder resin, and the pigment is the composite pigment of the present invention, and the reflected light from the identification medium is a left circular polarizing plate and a right circular polarizing plate. Observe through the board.
  • the reflected light is the reflected light when the identification medium is irradiated with natural light. Natural light means unpolarized light, and may be sunlight or artificial light.
  • the polarized light reflected by the identification medium depending on the twisting direction of the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment contained in the composite pigment of the present invention is as follows. (1) When the twisting directions of the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment are the same as each other: The identification medium is only circular polarization in the same direction as the twisting direction of the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment. reflect.
  • the identification medium reflects one circular polarization which is the same direction as the twisting direction of the first cholesteric liquid crystal pigment, and the second cholesteric. It reflects the other circular polarization that is in the same direction as the twisting direction of the liquid crystal pigment.
  • the identification medium when the identification medium is observed with the left circular polarizing plate and the right circular polarizing plate, the light reflected by the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment contains only one of the circular polarizations.
  • the reflected light of the identification medium is visually recognized by the one circular polarizing plate that transmits the one circular polarization, and the reflected light of the identification medium is not visually recognized or difficult to be visually recognized by the other circular polarizing plate.
  • the identification medium can be determined to be genuine.
  • the identification medium does not have a selective reflection function for selectively reflecting circular polarization, and the identification medium. Can be determined not to be genuine.
  • one circular polarizing plate transmits the light reflected by the first cholesteric liquid crystal pigment and is transmitted by the second cholesteric liquid crystal pigment. Does not transmit the reflected light. Therefore, when the identification medium is observed from the vicinity in the front direction with one of the circularly polarizing plates, the light reflected by the first cholesteric liquid crystal pigment is visually recognized as the reflected light of the identification medium, but is reflected by the second cholesteric liquid crystal resin. Since the light does not pass through one of the circularly polarizing plates, the reflected light of the identification medium is not visible or is difficult to see.
  • the other circular polarizing plate does not transmit the light reflected by the first cholesteric liquid crystal pigment, but transmits the light reflected by the second cholesteric liquid crystal pigment. Therefore, when the identification medium was observed from the vicinity in the front direction with the other circularly polarizing plate, the light reflected by the first cholesteric liquid crystal pigment did not pass through the other circularly polarizing plate and was reflected by the second cholesteric liquid crystal pigment. The light is visually recognized as the reflected light of the identification medium.
  • the identification medium does not have a selective reflection function that selectively reflects circular polarization, and the identification medium is genuine. It can be determined that it is not.
  • Step 2 is a step of visually observing the identification medium and determining whether or not the color derived from the second cholesteric liquid crystal pigment is visible.
  • the composite pigment of the present invention contained in the identification medium includes the second cholesteric liquid crystal pigment and the first cholesteric liquid crystal pigment of more than 0% by weight and 30% by weight or less based on the total amount of the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment. include.
  • an identification medium of the present invention is visually observed, as described below, the color derived from the second cholesteric liquid crystal pigment is visible, but the color derived from the first cholesteric liquid crystal pigment is not visible or visually recognized. It's hard to do.
  • the content of the first cholesteric liquid crystal pigment is smaller than the content of the second cholesteric liquid crystal pigment, so that it is difficult to visually recognize the circular polarization component reflected by the first cholesteric liquid crystal pigment by visual observation. Become. As a result, when the identification medium is visually observed, the color derived from the second cholesteric liquid crystal pigment is visible, but the color derived from the first cholesteric liquid crystal pigment is not visible or is difficult to see.
  • the identification medium By visually observing the identification medium, when the color derived from the second cholesteric liquid crystal pigment cannot be visually recognized, and the color derived from the second cholesteric liquid crystal pigment and the color derived from the first cholesteric liquid crystal pigment can be recognized to the extent that they can be distinguished. In that case, it can be determined that it is not genuine.
  • Whether or not the color derived from the second cholesteric liquid crystal pigment and the color derived from the first cholesteric liquid crystal pigment can be recognized to a distinguishable degree may be quantitatively evaluated using a spectrophotometer or the like.
  • a spectrophotometer any system can be used, for example, an XYZ color system, an L * a * b * color system, or the like can be used.
  • Step 3 is a step of observing the identification medium with a microscope and determining whether or not both the color derived from the first cholesteric liquid crystal pigment and the color derived from the second cholesteric liquid crystal pigment are visible.
  • the magnification in microscopic observation is preferably 50 or more, more preferably 100 or more, preferably 1000 or less, and more preferably 500 or less.
  • the magnification in microscopic observation is at least the above lower limit value, the color derived from the first cholesteric liquid crystal pigment becomes easily visible.
  • the colors derived from the first cholesteric liquid crystal pigment and the colors derived from the second cholesteric liquid crystal pigment are derived regardless of whether the twisting directions of the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment are the same or different from each other. Both colors are visible.
  • the identification medium of the present invention has a first cholesteric liquid pigment having a central wavelength of the selective reflection band in the wavelength range of 400 nm or more and 800 nm or less and having a selective reflection bandwidth of 150 nm or less, and a wavelength in the range of 400 nm or more and 800 nm or less. Since it contains a composite pigment containing a second cholesteric liquid pigment having a selective reflection bandwidth of 200 nm or more in a predetermined ratio, the color derived from the first cholesteric liquid pigment having a narrow selective reflection band can be visually recognized or not visually observed. It is difficult to do, but it can be made visible by microscopic observation. As a result, according to the present invention, the criterion for authenticity is increased, which can improve the anti-counterfeiting effect.
  • the full width at half maximum of the selective reflection band as the selective reflection bandwidth was obtained. That is, in the reflection spectrum, the base having the minimum intensity and the peak having the maximum intensity are determined, and the wavelength ⁇ 1 on the short wavelength side and the wavelength ⁇ 1 on the long wavelength side of the peak showing the intensity of the minimum intensity + (maximum intensity-minimum intensity) / 2.
  • the wavelength ⁇ 2 of the above was determined, and the average value (( ⁇ 1 + ⁇ 2) / 2) of these was used as the center wavelength of the selective reflection band of the cholesteric liquid crystal resin (pigment). Further, the wavelength ⁇ 2 to the wavelength ⁇ 1 was defined as the selective reflection band, and the width thereof (difference between ⁇ 2 and ⁇ 1: ⁇ ) was defined as the selective reflection bandwidth.
  • the particle size distribution of each pigment was measured by the laser / scattering method, and the average particle size was measured from the particle size distribution.
  • a laser diffraction / scattering type particle size distribution measuring device LA-960 manufactured by HORIBA, Ltd.
  • the twisting direction of each pigment is determined by transmitting the reflected light through the left and right circular polarizing plates when unpolarized light is incident on the multilayer films A to E (films containing each pigment) obtained in Production Examples 1 to 5. It was done by observing. That is, the multilayer film was irradiated with non-polarized light from the observer side, and the reflected light reflected by the multilayer film and reaching the observer side was observed. When the reflected light was right-handed circularly polarized light, it was judged to be right-handed twist, and when it was left-handed circularly polarized light, it was judged to be left-handed twisted.
  • the identification medium to be evaluated was visually observed under natural light, and it was evaluated whether or not the color derived from the first cholesteric liquid crystal pigment was visible. If it was visible, it was judged to be visible, and if it was difficult to see, it was judged to be invisible if it was not visible.
  • S ( ⁇ ) is the spectrum of the light source, and the value of the C light source was used in this embodiment. Further, x ( ⁇ ), y ( ⁇ ), and z ( ⁇ ) represent color matching functions.
  • X n, Y n, Z n respectively are the tristimulus values calculated from equation (17) in equation (19).
  • f (X / X n ), f (Y / Y n ), and f (Z / Z n ) are represented by the formulas (20) to (22), respectively.
  • ⁇ a * b * was calculated from the obtained values of a * and b * in each example using the following formula (23).
  • ⁇ a * b * ((a * 1- a * 2 ) 2 + (b * 1- b * 2 ) 2 ) 1/2 ... (23)
  • a * 1 is in each example a *
  • a * 2 is a * of comparative example 1
  • b * 1 is b * of each example
  • b * 2 denotes a b * Comparative Example 1.
  • ⁇ a * b * When ⁇ a * b * is less than 10, it is difficult to recognize the difference between the color derived from the first cholesteric liquid crystal pigment and the color derived from the second cholesteric liquid crystal pigment, and when it is 5 or less, the difference in color is further recognized. It will be difficult. When ⁇ a * b * is 10 or more, the difference between the color derived from the first cholesteric liquid crystal pigment and the color derived from the second cholesteric liquid crystal pigment can be recognized.
  • the coating liquid L1 was applied onto the rubbing-treated surface of the support to form a layer (coating layer) of the liquid crystal composition.
  • the coating liquid L1 was applied by adjusting the discharge amount with a die coater so that the film thickness of the layer of the liquid crystal composition before drying was 15 ⁇ m.
  • the layer side of the liquid crystal composition was irradiated with ultraviolet rays using a high-pressure mercury lamp to polymerize the layers of the liquid crystal composition.
  • the cholesteric liquid crystal composition is cured while maintaining the cholesteric regularity, and the cholesteric liquid crystal which is a layer of the resin having cholesteric regularity is cured.
  • a thin film of resin was formed.
  • a multi-layer film A having a structure of (support) / (thin film of cholesteric liquid crystal resin) was obtained.
  • the thickness of the thin film of the cholesteric liquid crystal resin of the multilayer film A was 3 ⁇ m.
  • Production Example 2 Production of Multilayer Film B as a Material for Pigment B
  • (1-1. Coating step) the coating liquid L2 obtained by mixing the materials shown in the following table was used instead of the coating liquid L1, and the coating liquid L2 was applied.
  • the same operation as in (1-1) of Production Example 1 was performed except that the discharge amount was adjusted so that the film thickness of the coating layer before drying was 25 ⁇ m, and the liquid crystal composition was placed on the support. A layer was formed.
  • the conditions for the first ultraviolet irradiation treatment were an illuminance of 5 mW / cm 2 at a wavelength of 365 nm and an exposure amount of 300 mJ / cm 2 at a wavelength of 365 nm under an atmospheric atmosphere.
  • the conditions for the second ultraviolet irradiation treatment were an illuminance of 30 mW / cm 2 at a wavelength of 365 nm and an exposure amount of 1800 mJ / cm 2 at a wavelength of 365 nm under an atmospheric atmosphere.
  • the heat treatment was carried out in an oven.
  • the cholesteric liquid crystal composition is cured while maintaining the cholesteric regularity, and the cholesteric liquid crystal which is a layer of the resin having cholesteric regularity is cured.
  • a thin film of resin was formed.
  • a multi-layer film B having a composition of (support) / (thin film of cholesteric liquid crystal resin) was obtained.
  • the thickness of the thin film of the cholesteric liquid crystal resin of the multilayer film B was 5 ⁇ m.
  • Production Example 3 Production of Multilayer Film C as a Material for Pigment C
  • the same operation as in Production Example 1 was performed except that the coating liquid L3 obtained by mixing the materials shown in the following table was used instead of the coating liquid L1 to obtain a multilayer film C.
  • the thickness of the thin film of the cholesteric liquid crystal resin of the multilayer film C was 3 ⁇ m.
  • Production Example 4 Production of Multilayer Film D as a Material for Pigment D
  • the same operation as in Production Example 1 was performed except that the coating liquid L4 obtained by mixing the materials shown in the following table was used instead of the coating liquid L1 to obtain a multilayer film D.
  • the thickness of the thin film of the cholesteric liquid crystal resin of the multilayer film D was 3 ⁇ m.
  • Production Example 5 Production of Multilayer Film E as a Material for Pigment E
  • the same operation as in Production Example 1 was performed except that the coating liquid L5 obtained by mixing the materials shown in the following table was used instead of the coating liquid L1 to obtain a multilayer film E.
  • the thickness of the thin film of the cholesteric liquid crystal resin of the multilayer film E was 3 ⁇ m.
  • the compound (3) contained in the coating liquid L5 is a compound represented by the following formula.
  • the corner portion 135 of the bar 134 was set so that the multilayer film 110 could be folded back at an angle ⁇ (60 °).
  • the multi-layer film 110 can be folded back from the support 111 (PET film) by removing the thin film 112 of the first cholesteric liquid crystal resin (or the thin film of the second cholesteric liquid crystal resin) from the film delivery portion 120.
  • the multilayer film 110 was attached in such an orientation.
  • the multilayer film 110 was sent out from the film feeding unit 120 in a state where the film collecting unit 140 applied tension to the multilayer film 10 in the transport direction.
  • the magnitude of the tension applied to the multilayer film 110 was set to 80 N / m.
  • air was injected from the nozzle 436 at a pressure of 0.5 MPa.
  • the multilayer film 110 was folded back at the corner portion 135 of the bar 134, and many cracks were formed. After that, the thin film 112 of the first cholesteric liquid crystal resin (or the thin film of the second cholesteric liquid crystal resin) in which the cracks were formed was peeled off and blown off by the air ejected from the nozzle 136, and the peeled piece 111A was obtained.
  • the stripped piece 111A was recovered, pulverized with a cutter mill, classified using a 51 ⁇ m sieve, and only the particles that passed through the sieve were recovered to obtain a pigment.
  • the average particle size of the obtained pigment, the center wavelength of the selective reflection band, the selective reflection band and the selective reflection bandwidth were measured.
  • the results are shown in Tables 5 and 6. From these measurement results, the pigments A, C, D and E have a central wavelength of the selective reflection band in the wavelength range of 400 nm or more and 800 nm or less, and the selective reflection bandwidth is 150 nm or less as the first cholesteric liquid crystal pigment.
  • Pigment B was a second cholesteric liquid crystal pigment having a selective reflection bandwidth of 200 nm or more within a wavelength range of 400 nm or more and 800 nm or less.
  • the color derived from pigment A was green, the color derived from pigment B was silver, the color derived from pigment C was blue, the color derived from pigment D was red, and the color derived from pigment E was red.
  • Examples 1 to 7, Comparative Example 2 (Preparation of ink composition)
  • the ink composition is prepared by the following method using the pigments A, C, D or E produced in Production Example 6 as the first cholesteric liquid crystal pigment and the pigment B produced in Production Example 6 as the second cholesteric liquid crystal pigment.
  • the first cholesteric liquid crystal pigment, the second cholesteric liquid crystal pigment, and the binder (UV curable binder, "Recure OP 4300-2" series FG-20SC thick medium manufactured by Jujo Chemical Co., Ltd.) shown in Tables 6 and 7 are mixed.
  • An ink composition having a solid content concentration of 10% was prepared.
  • the content of the first cholesteric liquid crystal pigment with respect to the total amount of the first cholesteric liquid crystal pigment and the second cholesteric liquid crystal pigment is the amount shown in Tables 6 and 7 (described as "content of the first cholesteric liquid crystal pigment" in the table). I tried to become.
  • the prepared ink composition was screen-printed on a base material (black paper).
  • a screen plate a screen plate having 120 thousands per inch was used.
  • the printed surface of the base material was irradiated with ultraviolet rays using a high-pressure mercury lamp to obtain an identification medium.
  • the illuminance at a wavelength of 365 nm was 280 mW / cm 2 and the exposure amount at a wavelength of 365 nm was 400 mJ / cm 2 under a nitrogen gas atmosphere having an oxygen concentration of 400 ppm or less.
  • the obtained identification medium was visually observed, evaluated by a spectrophotometer, observed under a microscope, and observed with a polarizing plate.
  • Example 1 An identification medium was obtained by performing the same operation as in Example 1 except that the first cholesteric liquid crystal pigment was not used in the preparation of the ink composition of Example 1. The obtained identification medium was visually observed, evaluated by a spectrophotometer, observed under a microscope, and observed with a polarizing plate.
  • the following table shows the pigment information (type, center wavelength of the selective reflection band, selective reflection band, selective reflection bandwidth, average particle size, and twisting direction) of the pigments used in each example together with the evaluation results of the examples and the comparative examples.

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  • Liquid Crystal Substances (AREA)

Abstract

L'invention concerne un pigment composite qui contient un premier et un second pigment cristallin liquide cholestérique. Ledit premier pigment cristallin liquide cholestérique possède une longueur d'onde centrale dans une bande de réflexion sélective à l'intérieur d'une plage de longueurs d'ondes supérieure ou égale à ４００ｎｍ et inférieure ou égale à ８００ｎｍ, et présente une largeur de bande de réflexion sélective inférieure ou égale à １５０ｎｍ. Ledit second pigment cristallin liquide cholestérique possède une largeur de bande de réflexion sélective supérieure ou égale à 200nm à l'intérieur d'une plage de longueurs d'ondes supérieure ou égale à ４００ｎｍ et inférieure ou égale à ８００ｎｍ. La bande de réflexion sélective dudit premier pigment cristallin liquide cholestérique et la bande de réflexion sélective dudit second pigment cristallin liquide cholestérique, se superposent au moins partiellement. La teneur en premier pigment cristallin liquide cholestérique dépasse 0% en masse et est inférieure ou égale à 30% en masse pour la quantité totale desdits premier et second pigments cristallins liquides cholestériques.
PCT/JP2020/028316 2019-07-30 2020-07-21 Pigment composite, support d'identification, et procédé de jugement d'authentification WO2021020243A1 (fr)

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CN202080053840.8A CN114207084A (zh) 2019-07-30 2020-07-21 复合颜料、识别介质及真实性判断方法
JP2021536979A JPWO2021020243A1 (fr) 2019-07-30 2020-07-21
EP20846442.0A EP4006107A4 (fr) 2019-07-30 2020-07-21 Pigment composite, support d'identification, et procédé de jugement d'authentification
US17/629,861 US20220275213A1 (en) 2019-07-30 2020-07-21 Composite pigment, identification medium, and method for determining authenticity

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Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0672962A (ja) 1992-08-28 1994-03-15 Asahi Denka Kogyo Kk 光学活性フェニル化合物
JPH1180733A (ja) * 1997-06-19 1999-03-26 Consortium Elektrochem Ind Gmbh 光重合可能なコレステリック液晶のコレステリック反射帯域を拡張する方法およびこの方法により製造した光学素子
JP2000290315A (ja) 1999-04-08 2000-10-17 Asahi Denka Kogyo Kk 重合性光学活性化合物
JP2001261739A (ja) * 2000-03-16 2001-09-26 Merck Patent Gmbh 広帯域液晶顔料
US6468444B1 (en) 1999-03-25 2002-10-22 Basf Aktiengesellschaft Chiral compounds and their use as chiral dopants for producing cholesteric liquid crystal compositions
JP2003066214A (ja) 2001-08-22 2003-03-05 Fuji Photo Film Co Ltd コレステリック液晶カラーフィルタの製造方法
JP2003073600A (ja) 2001-05-23 2003-03-12 Toppan Printing Co Ltd 偽造防止インキ及び偽造防止印刷物並びにその真偽判定方法
JP2003145912A (ja) * 2001-11-15 2003-05-21 Toppan Printing Co Ltd 偽造防止印刷物
JP2003313187A (ja) 2002-04-18 2003-11-06 Fuji Photo Film Co Ltd 光学活性イソソルビド誘導体及びその製造方法、光反応型キラル剤、液晶組成物、液晶カラーフィルター、光学フィルム及び記録媒体、並びに液晶の螺旋構造を変化させる方法、液晶の螺旋構造を固定化する方法
JP2003342219A (ja) 2002-05-27 2003-12-03 Asahi Denka Kogyo Kk 光学活性化合物及び該化合物を含有した液晶組成物
JP2004115414A (ja) 2002-09-25 2004-04-15 Asahi Denka Kogyo Kk 光学活性化合物及び該光学活性化合物を含有した液晶組成物
JP2005289881A (ja) 2004-03-31 2005-10-20 Asahi Denka Kogyo Kk 光学活性化合物及び該化合物を含有した液晶組成物
JP2007176870A (ja) 2005-12-28 2007-07-12 Nippon Zeon Co Ltd キラル剤
JP2009541047A (ja) * 2006-06-27 2009-11-26 シクパ・ホールディング・ソシエテ・アノニム コレステリック多層
JP2010196005A (ja) * 2009-02-27 2010-09-09 Dainippon Printing Co Ltd 色彩可変インキ組成物
JP2014189677A (ja) * 2013-03-27 2014-10-06 Fujifilm Corp 光干渉顔料およびその製造方法
JP2015027743A (ja) 2013-07-30 2015-02-12 日本ゼオン株式会社 樹脂薄膜の剥離片の製造方法、樹脂薄膜顔料の製造方法、塗料、偽造防止物品、セキュリティ物品及び加飾性物品
US9800428B2 (en) 2013-02-20 2017-10-24 Panasonic Intellectual Property Corporation Of America Control method for information apparatus and computer-readable recording medium
WO2018034215A1 (fr) * 2016-08-19 2018-02-22 日本ゼオン株式会社 Support d'affichage pour évaluation et son procédé de fabrication

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101617025B (zh) * 2007-02-22 2013-12-25 日本瑞翁株式会社 胆甾相液晶组合物、圆偏振光分离片及其制造方法
JP6159081B2 (ja) * 2012-12-17 2017-07-05 富士フイルム株式会社 コレステリック液晶積層体およびその製造方法ならびにコレステリック液晶積層体の組合せ体

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0672962A (ja) 1992-08-28 1994-03-15 Asahi Denka Kogyo Kk 光学活性フェニル化合物
JPH1180733A (ja) * 1997-06-19 1999-03-26 Consortium Elektrochem Ind Gmbh 光重合可能なコレステリック液晶のコレステリック反射帯域を拡張する方法およびこの方法により製造した光学素子
US6468444B1 (en) 1999-03-25 2002-10-22 Basf Aktiengesellschaft Chiral compounds and their use as chiral dopants for producing cholesteric liquid crystal compositions
JP2000290315A (ja) 1999-04-08 2000-10-17 Asahi Denka Kogyo Kk 重合性光学活性化合物
JP2001261739A (ja) * 2000-03-16 2001-09-26 Merck Patent Gmbh 広帯域液晶顔料
JP2003073600A (ja) 2001-05-23 2003-03-12 Toppan Printing Co Ltd 偽造防止インキ及び偽造防止印刷物並びにその真偽判定方法
JP2003066214A (ja) 2001-08-22 2003-03-05 Fuji Photo Film Co Ltd コレステリック液晶カラーフィルタの製造方法
JP2003145912A (ja) * 2001-11-15 2003-05-21 Toppan Printing Co Ltd 偽造防止印刷物
JP2003313187A (ja) 2002-04-18 2003-11-06 Fuji Photo Film Co Ltd 光学活性イソソルビド誘導体及びその製造方法、光反応型キラル剤、液晶組成物、液晶カラーフィルター、光学フィルム及び記録媒体、並びに液晶の螺旋構造を変化させる方法、液晶の螺旋構造を固定化する方法
JP2003342219A (ja) 2002-05-27 2003-12-03 Asahi Denka Kogyo Kk 光学活性化合物及び該化合物を含有した液晶組成物
JP2004115414A (ja) 2002-09-25 2004-04-15 Asahi Denka Kogyo Kk 光学活性化合物及び該光学活性化合物を含有した液晶組成物
JP2005289881A (ja) 2004-03-31 2005-10-20 Asahi Denka Kogyo Kk 光学活性化合物及び該化合物を含有した液晶組成物
JP2007176870A (ja) 2005-12-28 2007-07-12 Nippon Zeon Co Ltd キラル剤
JP2009541047A (ja) * 2006-06-27 2009-11-26 シクパ・ホールディング・ソシエテ・アノニム コレステリック多層
JP2010196005A (ja) * 2009-02-27 2010-09-09 Dainippon Printing Co Ltd 色彩可変インキ組成物
US9800428B2 (en) 2013-02-20 2017-10-24 Panasonic Intellectual Property Corporation Of America Control method for information apparatus and computer-readable recording medium
JP2014189677A (ja) * 2013-03-27 2014-10-06 Fujifilm Corp 光干渉顔料およびその製造方法
JP2015027743A (ja) 2013-07-30 2015-02-12 日本ゼオン株式会社 樹脂薄膜の剥離片の製造方法、樹脂薄膜顔料の製造方法、塗料、偽造防止物品、セキュリティ物品及び加飾性物品
WO2018034215A1 (fr) * 2016-08-19 2018-02-22 日本ゼオン株式会社 Support d'affichage pour évaluation et son procédé de fabrication

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4006107A4

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CN114207084A (zh) 2022-03-18
EP4006107A4 (fr) 2023-08-02

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